EP0038459A1 - Process for the prevention of reversion during the manufacture of rubber vulcanisates - Google Patents
Process for the prevention of reversion during the manufacture of rubber vulcanisates Download PDFInfo
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- EP0038459A1 EP0038459A1 EP81102569A EP81102569A EP0038459A1 EP 0038459 A1 EP0038459 A1 EP 0038459A1 EP 81102569 A EP81102569 A EP 81102569A EP 81102569 A EP81102569 A EP 81102569A EP 0038459 A1 EP0038459 A1 EP 0038459A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/38—Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
Definitions
- the invention relates to a vulcanization system consisting of sulfur and / or a sulfur donor, a mercapto or sulfenamide accelerator, a compound which contains a thiophenyl radical and a conventional additional accelerator, a vulcanizable rubber mixture consisting of natural and / or synthetic rubber , the above vulcanization system and usual additives, as well as a method for their vulcanization.
- the vulcanization systems according to the invention can be used to vulcanize rubbers which, after vulcanization, have improved reversion resistance.
- Reversion is understood to mean a decrease in the degree of crosslinking and mechanical values of vulcanizates (such as tensile strength, tear propagation resistance, elasticity) if the vulcanization continues beyond the optimum. Reversion occurs in the vul Canation of diene rubbers, especially natural rubber and synthetic polyisoprene, at high vulcanization temperatures or long ones. Vulcanization times, as they are required for the production of bulky items (e.g. truck tires). The use of economically desirable high vulcanization temperatures is limited by the occurrence of reversion.
- vulcanization accelerator used has an influence on the reversion resistance of the rubber mixtures. While ultra accelerators such as dithiocarbamates, thiurams and basic accelerators such as diphenylguanidine give low reversion resistance, mercapto accelerators such as mercaptobenzthiazole, dibenzothiazyl disulfide and the zinc salt of mercaptobenzothiazole, or sulfenamide accelerators such as benzothiazylsulyl-2-cyclo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hex
- the object of the invention was therefore to provide a vulcanization system which increases the resistance to reversion of the rubber vulcanizates and at the same time does not shorten the vulcanization time during their vulcanization.
- the sum of components a - d) is 100 parts by weight.
- halogen examples include chlorine, bromine and iodine.
- the alkyl radicals of C 1 -C 4 can be: methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, tert-butyl.
- the alkoxy radicals can represent, for example: methoxy, ethoxy, propoxy or butyloxy.
- the alkylene radicals of C 1 -C 12 can be: methylene, ethylene, 1,2- and 1,3-propylene, butylene, pentylene, hexylene, octylene, nonylene, decylene, undecylene, dodecylene.
- alkyl radicals with C1-C12 can easily be derived from the alkylene radicals mentioned.
- Cycloalkylene can be from C 4 -C 12 , such as cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, cyclodecylene, cycloundecylene, cyclododecylene.
- Arylene can be phenylene and naphthylene.
- Arylalkylene should be in the range C 8 -C 12 and represent, for example, o, m, p-xylylene and the isomeric naphthalene dimethyl derivatives.
- Another object of the invention is a vulcanizable mixture consisting of natural and / or synthetic rubber from halogen-free dienes, the above vulcanization system and optionally other conventional additives.
- the compounds d) can be used in pure form. But it is also conceivable that mixtures of these products can be used.
- DTDM Dimorpholyl disulfide
- TMTD tetramethylthiuram disulfide
- 2- (N-morpholinyldithio) benzothiazole e.g. Dimorpholyl disulfide (DTDM), tetramethylthiuram disulfide (TMTD) or 2- (N-morpholinyldithio) benzothiazole.
- Examples of accelerators of the mercapto group in b) are: 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS) or the zinc salt of 2-mercaptobenzothiazole (ZMBT).
- MBT 2-mercaptobenzothiazole
- MBTS dibenzothiazyl disulfide
- ZMBT zinc salt of 2-mercaptobenzothiazole
- accelerators of the sulfenamide group in b) are: benzothiazyl-2-cyclohexylsulfen- amide (CBS), benzothiazyl-2-tert-butylsulfenamide (TBBS), benzothiazyl-2-morpholine sulfenamide (MBS), 2- (N-morpholinyl-dithio) -benzenethiazole (MBSS) or morpholinyl-thiocarbonyl-sulfenmorpholide (OTOS).
- MBT MBT, MBTS, CBS, TBBS and MBS are preferred.
- Examples of conventional additional accelerators in c) are: tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), zinc-N-dimethyldithiocarbamate (ZDMC), zinc-N-diethyl-dithiocarbamate (ZDEC), zinc-N-dibutylate ZDBC), zinc N-ethylphenyldithiocarbamate (ZEPC) or zinc N-penta-methylene dithiocarbamate (Z5MC).
- TMTD tetramethylthiuram disulfide
- TMTM tetramethylthiuram monosulfide
- ZDMC zinc-N-dimethyldithiocarbamate
- ZDEC zinc-N-diethyl-dithiocarbamate
- ZDBC zinc-N-dibutylate ZDBC
- ZPC zinc N-ethylphenyldithiocarbamate
- the vulcanization systems according to the invention have advantages in terms of resistance to reversion after a longer vulcanization time and / or high vulcanization temperatures (for example 45 minutes at 180 ° C.), in terms of mechanical values such as tension value, tensile strength, elongation at break, hardness, elasticity, tear resistance, wear resistance, fatigue resistance, internal heat generation ( heat build-up), dynamic flow and abrasion.
- the individual components of the vulcanization system can either separate the diene rubbers or rubber mixtures before vulcanization or in the form of a mixture or a rubber accelerator premix (see: Ullmann's Encyklopadie der techn. Chemie, 3rd edition, Verlag Urban & Schwarzenberg, Kunststoff -Berlin 1957, Volume 9, p. 364) can be added.
- the diene rubbers can do it all. usual additives such as fillers, in particular carbon blacks, mineral oils, plasticizers, tackifiers, acceleration activators, in particular stearic acid, waxes, anti-aging agents, anti-ozone agents, blowing agents, dyes, pigments.
- fillers in particular carbon blacks, mineral oils, plasticizers, tackifiers, acceleration activators, in particular stearic acid, waxes, anti-aging agents, anti-ozone agents, blowing agents, dyes, pigments.
- Fillers such as the types of carbon black used in the rubber processing industry, as well as silica, in particular fine-particle silica obtained in the gas phase, and hydrophobic silica and fine-particle metal oxides, including mixed oxides and oxide mixtures, are valuable components of the mixture.
- the vulcanization of the diene rubbers is generally carried out at temperatures between 100 ° C. and about 300 ° C., preferably at 140-240 ° C.
- temperatures between 100 ° C. and about 300 ° C., preferably at 140-240 ° C.
- vulcanization processes customary in technology such as press heating, heating with superheated steam, hot air, salt bath, fluidized bed, ultra-high frequency and steam pipe are used.
- the invention is illustrated by the following examples:
- System 3 gives significantly better reversion resistance (after over-vulcanization of 45 '/ 180 ° C) than the system 2 containing zinc dibutyl dithiophosphate and results in a significantly higher scorch resistance at 130 ° C than system 2.
- a rubber premix was made in the internal mixer using the following ingredients:
- the vulcanization system 2 according to the invention has clear advantages over the comparison system 2 with regard to resistance to reversion after over-vulcanization at 180 ° C.
- Example 4 A rubber premix based on natural rubber was produced in an internal mixer from the constituents listed in Example 3. The following were mixed on a rolling mill:
- the additional accelerators according to the invention used in Example 4, which correspond to general formula 1, are:
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Abstract
Description
Die Erfindung betrifft ein Vulkanisationssystem, bestehend aus Schwefel, und/oder einem Schwefelspender, einem Mercapto- bzw. Sulfenamid-Beschleuniger, einer Verbindung, die einen Thiophenylrest enthält, und einem üblichen Zusatzbeschleuniger, eine vulkanisierbare Kautschukmischung, bestehend aus Natur- und/oder Synthesekautschuk, dem obigen Vulkanisationssystem sowie üblichen Zusätzen, sowie ein Verfahren zu ihrer Vulkanisation.The invention relates to a vulcanization system consisting of sulfur and / or a sulfur donor, a mercapto or sulfenamide accelerator, a compound which contains a thiophenyl radical and a conventional additional accelerator, a vulcanizable rubber mixture consisting of natural and / or synthetic rubber , the above vulcanization system and usual additives, as well as a method for their vulcanization.
Mit Hilfe der erfindungsgemäßen Vulkanisationssysteme lassen sich Kautschuke vulkanisieren, die nach erfolgter Vulkanisation eine verbesserte Reversionsbeständigkeit besitzen.The vulcanization systems according to the invention can be used to vulcanize rubbers which, after vulcanization, have improved reversion resistance.
Unter Reversion versteht man ein Wiederabfallen des Vernetzungsgrades und mechanischer Werte von Vulkanisaten (wie Zugfestigkeit, Weiterreißfestigkeit, Elastizität) bei einer Fortführung der Vulkanisation über das Optimum hinaus. Reversion tritt auf bei der Vulkanisation von Dien-Kautschuken, insbesondere Naturkautschuk und synthetischem Polyisopren, bei hohen.Vulkanisationstemperaturen bzw. langen. Vulkanisationszeiten, wie sie bei der Herstellung voluminöser Artikel (z.B. LKW-Reifen) erforderlich sind. Die Anwendung wirtschaftlich wünschenswerter hoher Vulkänisationstemperaturen wird durch das Auftreten der Reversion begrenzt.Reversion is understood to mean a decrease in the degree of crosslinking and mechanical values of vulcanizates (such as tensile strength, tear propagation resistance, elasticity) if the vulcanization continues beyond the optimum. Reversion occurs in the vul Canation of diene rubbers, especially natural rubber and synthetic polyisoprene, at high vulcanization temperatures or long ones. Vulcanization times, as they are required for the production of bulky items (e.g. truck tires). The use of economically desirable high vulcanization temperatures is limited by the occurrence of reversion.
Eine Verbesserung der Reversionsbeständigkeit war bisher nur in sehr begrenztem Umfang möglich.Up until now, an improvement in the resistance to reversion was only possible to a very limited extent.
Es ist bekannt, daß die Reversionsbeständigkeit.von Vulkanisationssystemen.verbessert werden kann durch Verwendung verringerter Schwefel-Dosierungen. Während bei der "Normal-Schwefel-Vulkanisation" Schwefel-Mengen von ca. 1,8 - 2,5 phr (Gew.-Teile, bezogen auf 100 Gew.-Teile Kautschuk) verwendet werden, arbeiten "Semi-Efficient-Systeme" mit mittleren Schwefel-Mengen von ca. 1 - 1,8 phr und "Efficient-Systeme" mit Schwefel-Dosierungen von unter 1 phr. Im Vergleich zur Normal-Schwefel-Vulkanisation treten mit verringerten Schwefel-Mengen jedoch Nachteile auf hinsichtlich Rißbeständigkeit, Weiterreißfestigkeit, Abriebbeständigkeit und Cordhaftung der Vulkanisate, was die Anwendung der Vulkanisation mit niederen bzw. mittleren Schwefel-Mengen begrenzt. Es ist z.B. bei der Reifen-Herstellung nicht möglich, die Schwefel-Dosierung unter den Bereich mittlerer Dosierungen (ca. 1,5) zu senken.It is known that the resistance to reversion of vulcanization systems can be improved by using reduced doses of sulfur. While "normal sulfur vulcanization" uses sulfur amounts of approx. 1.8 - 2.5 phr (parts by weight, based on 100 parts by weight of rubber), "semi-efficient systems" work with average sulfur amounts of approx. 1 - 1.8 phr and "efficient systems" with sulfur doses of less than 1 phr. In comparison to normal sulfur vulcanization, however, with reduced sulfur amounts there are disadvantages with regard to crack resistance, tear propagation resistance, abrasion resistance and cord adhesion of the vulcanizates, which limits the use of vulcanization with low or medium amounts of sulfur. For example, in tire manufacture it is not possible to lower the sulfur dosage below the medium dosage range (approx. 1.5).
Es ist weiter bekannt, daß die Art der verwendeten Vulkanisationsbeschleuniger einen Einfluß auf die Reversionsbeständigkeit der Kautschukmischungen hat. Während Ultra-Beschleuniger wie Dithiocarbamate, Thiurame, sowie basische Beschleuniger wie Diphenylguanidin, niedrige Reversionsbeständigkeit ergeben, verhalten sich Mercapto-Beschleuniger wie Mercaptobenzthiazol, Dibenzothiazyldisulfid und das Zinksalz des Mercaptobenzthiazols, bzw. Sulfenamid-Beschleuniger wie Benzothiazyl-2-cyclo- hexylsulfenamid, Benzothiazyl-2-tert.-butylsulfenamid, Benzothiazyl-2-morpholin-sulfenamid und Benzothiazyldicyclohexylsulfenamid günstiger hinsichtlich Reversionsbeständigkeit.It is also known that the type of vulcanization accelerator used has an influence on the reversion resistance of the rubber mixtures. While ultra accelerators such as dithiocarbamates, thiurams and basic accelerators such as diphenylguanidine give low reversion resistance, mercapto accelerators such as mercaptobenzthiazole, dibenzothiazyl disulfide and the zinc salt of mercaptobenzothiazole, or sulfenamide accelerators such as benzothiazylsulyl-2-cyclo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-hexo-cyclo-hexo-hexo-hexo-cyclo-hexo-hexo-hexo-cyclo-hexo-hexo-hexo-cyclo-hexo-cyclo-hexo-hexo-hexo-hexo-cyclo-hexo-hexo-cyclo-hexo-cyclo-hexo-cyclo-hexo-cyclo-hexo-hexo-cyclo-hexo-cyclo-hexo-oxo 2-tert-butylsulfenamide, benzothiazyl-2-morpholine-sulfenamide and benzothiazyldicyclohexylsulfenamide are more favorable with regard to reversion resistance.
Es ist daher Stand der Technik, Vulkanisationssysteme für Dien-Kautschuke mit verbesserter Reversionsbeständigkeit wie folgt aufzubauen:
- a) Mittlere Schwefel-Mengen (ca. 1,4 - 1,6 phr),
- b) Mercapto- bzw. Sulfenamid-Beschleuniger (ca. 1 - 2 phr).
- a) Medium amounts of sulfur (approx. 1.4 - 1.6 phr),
- b) Mercapto or sulfenamide accelerators (approx. 1 - 2 phr).
Jedoch ergeben auch derartige Vulkanisationssysteme bei hohen Vulkanisationstemperaturen (z.B. über 170°C) bzw. langer Heizdauer Reversion.However, such vulcanization systems also result in reversion at high vulcanization temperatures (e.g. above 170 ° C) or long heating times.
Es ist ferner bekannt, daß der Zusatz von Vulkanisationsbeschleunigern des Dithiophosphat-Typs wie Zinkdibutyl-dithiophosphat zu den oben beschriebenen Vulkanisationssystemen die Reversionsbeständigkeit verbessert (H. Ehrend, Gummi Asbest Kunststoffe 3 c (1977) S. 68 - 71). Diese Beschleuniger verbessern zwar die Reversion, verkürzen aber die Anvulkanisationszeit in unerwünschter Weise. Dies stellt einen Nachteil dar, weil eine ausreichende Verarbeitungssicherheit, insbesondere bei den Anwendungsgebieten erforderlich ist, bei denen eine Verbesserung der Reversionsbeständigkeit von besonderem Interesse ist, z.B. bei der Herstellung von LKW-Reifen und allgemein bei der Herstellung voluminöser Artikel.It is also known that the addition of vulcanization accelerators of the dithiophosphate type such as zinc dibutyl dithiophosphate to the Vul sewer systems improves the resistance to reversion (H. Ehrend, Gummi Asbestos Kunststoffe 3 c (1977) pp. 68 - 71). Although these accelerators improve reversion, they undesirably shorten the scorching time. This is a disadvantage because sufficient processing security is required, in particular in the fields of application in which an improvement in the resistance to reversion is of particular interest, for example in the production of truck tires and in general in the production of bulky articles.
Aufgabe der Erfindung war es somit, ein Vulkanisationssystem bereitzustellen, das die Reversionsbeständigkeit der Kautschukvulkanisate erhöht und gleichzeitig die Anvulkanisationszeit bei deren Vulkanisation nicht verkürzt.The object of the invention was therefore to provide a vulcanization system which increases the resistance to reversion of the rubber vulcanizates and at the same time does not shorten the vulcanization time during their vulcanization.
Gegenstand der Erfindung ist somit ein Vulkanisationssystem, bestehend aus
- a) 20 - 50 Gew.-Teilen, bevorzugt 40 - 50 Gew.-Teilen, Schwefel oder 20 - 50 Gew.-Teilen, bevorzugt 40 - ?0 Gew.-Teilen, eines Schwefelspenders,
- b) 20 - 50 Gew.-Teilen, bevorzugt 20 - 30 Gew.-Teilen, eines Beschleunigers der Mercapto- bzw. Sulfenamid-Gruppe,
- c) 0 - 10 Gew.-Teilen, bevorzugt 0 - 5 Gew.-Teilen, eines konventionellen Zusatzbeschleunigers, und
- d) 20 - 50 Gew.-Teilen, bevorzugt 20 - 30 Gew.-Teilen, einer Verbindung der allgemeinen Formel (1)
- R1 bis R5 gleich oder verschieden, Wasserstoff, Halogen, Nitro, Cyano, -CF3, -CCl3, Carboxyl, einen Alkoxyrest mit einem C1-C4-Alkylrest, wobei jedoch nicht alle Reste R1 - R5 gleichzeitig Wasserstoff darstellen, bedeuten
- X 1 - 4, bevorzugt 2 - 3 bedeutet,
- Y 0 oder 1 darstellt und
- Z divalente Reste darstellt, wie
- R 6 den Rest darstellt,
- R6 kann außerdem Alkyl mit C1-C12 und Cycloalkylen von C4-C12 sein, das gegebenenfalls substituiert ist durch -OH bzw. Alkoxy mit C1-C4 im Alkoxy-Rest.
- R6 kann ferner Benzyl oder Trichlormethyl sein.
- a) 20-50 parts by weight, preferably 40-50 parts by weight, sulfur or 20-50 parts by weight, preferably 40-0.0 parts by weight, of a sulfur donor,
- b) 20-50 parts by weight, preferably 20-30 parts by weight, of an accelerator from the mercapto or sulfenamide group,
- c) 0-10 parts by weight, preferably 0-5 parts by weight, of a conventional additional accelerator, and
- d) 20-50 parts by weight, preferably 20-30 parts by weight, of a compound of the general formula (1)
- R 1 to R 5 are the same or different, hydrogen, halogen, nitro, cyano, -CF 3 , -CCl 3 , carboxyl, an alkoxy radical with a C 1 -C 4 alkyl radical, but not all radicals R 1 - R 5 at the same time Represent hydrogen
- X is 1-4, preferably 2-3,
- Y represents 0 or 1 and
- Z represents divalent radicals, such as
- R 6 represents the remainder,
- R 6 can also be alkyl with C 1 -C 12 and cycloalkylene of C4-C 12 , which is optionally substituted by -OH or alkoxy with C 1 -C 4 in the alkoxy radical.
- R 6 can also be benzyl or trichloromethyl.
Die Summe der Komponenten a - d) beträgt 100 GewichtsTeile.The sum of components a - d) is 100 parts by weight.
Als Halogen seien beispielsweise Chlor, Brom, Jod genannt.Examples of halogen are chlorine, bromine and iodine.
Die Alkylreste von C1-C4 können sein:Methyl, Ethyl, iso-Propyl, n-propyl, n-Butyl, iso-Butyl, tert.-Butyl.The alkyl radicals of C 1 -C 4 can be: methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, tert-butyl.
Die Alkoxyreste können beispielsweise darstellen:Meth- oxy, Ethoxy, Propoxy oder Butyloxy.The alkoxy radicals can represent, for example: methoxy, ethoxy, propoxy or butyloxy.
Die Alkylenreste von C1-C12 können sein:Methylen, Ethylen, 1,2- und 1,3-Propylen, Butylen, Pentylen, Hexylen, Octylen, Nonylen, Decylen, Undecylen, Dodecylen.The alkylene radicals of C 1 -C 12 can be: methylene, ethylene, 1,2- and 1,3-propylene, butylene, pentylene, hexylene, octylene, nonylene, decylene, undecylene, dodecylene.
Die Alkylreste mit C1-C12 können aus den genannten Alkylenresten leicht abgeleitet werden.The alkyl radicals with C1-C12 can easily be derived from the alkylene radicals mentioned.
Cycloalkylen kann von C4-C12 sein, wie etwa Cyclobutylen, Cyclopentylen, Cyclohexylen, Cycloheptylen, Cyclooctylen, Cyclononylen, Cyclodecylen, Cycloundecylen, Cyclododecylen.Cycloalkylene can be from C 4 -C 12 , such as cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, cyclodecylene, cycloundecylene, cyclododecylene.
Arylen kann sein Phenylen und Naphthylen.Arylene can be phenylene and naphthylene.
Arylalkylen soll im Bereich C8-C12 liegen und beispielsweise o, m, p-Xylylen sowie die isomeren Napthalindimethyl-Derivate darstellen.Arylalkylene should be in the range C 8 -C 12 and represent, for example, o, m, p-xylylene and the isomeric naphthalene dimethyl derivatives.
Ein weiterer Gegenstand der Erfindung ist eine vulkanisierbare Mischung, bestehend aus natürlichem und/oder synthetischem Kautschuk aus halogenfreien Dienen, obigem Vulkanisationssystem und gegebenenfalls weiteren üblichen Zusätzen.Another object of the invention is a vulcanizable mixture consisting of natural and / or synthetic rubber from halogen-free dienes, the above vulcanization system and optionally other conventional additives.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Vulkanisation von Natur- und/oder Synthesekautschuk aus halogenfreien Dienen in Gegenwart von Schwefel und/oder Schwefelspendern, Vulkanisationsbeschleunigern und gegebenenfalls üblichen Zusätzen, das dadurch gekennzeichnet ist, daß man
- a) 0,1 - 5 phr, vorzugsweise 1 - 2 phr, Schwefel bzw. 0,2 - 10 phr, vorzugsweise 2 - 4 phr, eines Schwefelspenders,
- b) 0,1 - 5 phr, bevorzugt 0,4 - 2 phr, eines Beschleunigers der Mercapto- bzw. Sulfenamid-Gruppe,
- c) 0 - 5 phr, bevorzugt 0 - 1 phr, eines konventionellen Zusatzbeschleunigers, und
- d) 0,1 - 5 phr, bevorzugt 0,4 - 2,5 phr, einer Verbindung der allgemeinen Formel 1,
getrennt oder gleichzeitig dem Kautschuk zugibt und anschließend in üblicher Weise vulkanisiert.Another object of the invention is a process for the vulcanization of natural and / or synthetic rubber from halogen-free dienes in the presence of sulfur and / or sulfur donors, vulcanization accelerators and, if appropriate, conventional additives, which is characterized in that
- a) 0.1 to 5 phr, preferably 1 to 2 phr, sulfur or 0.2 to 10 phr, preferably 2 to 4 phr, of a sulfur donor,
- b) 0.1-5 phr, preferably 0.4-2 phr, of an accelerator from the mercapto or sulfenamide group,
- c) 0-5 phr, preferably 0-1 phr, of a conventional additional accelerator, and
- d) 0.1-5 phr, preferably 0.4-2.5 phr, of a compound of the general formula 1,
separately or simultaneously added to the rubber and then vulcanized in the usual manner.
Die Verbindungen d) können in reiner Form eingesetzt werden. Es ist aber auch denkbar, daß man Abmischungen dieser Produkte einsetzen kann.The compounds d) can be used in pure form. But it is also conceivable that mixtures of these products can be used.
Als Schwefelspender der Gruppe a) werden Verbindungen angesehen, die unter Vulkanisationsbedingungen Schwefel abspalten. Dies sind z.B. Dimorpholyldisulfid (DTDM), Tetramethylthiuramdisulfid (TMTD) oder 2-(N-Morpholinyldithio)-benzothiazol.Compounds which release sulfur under vulcanization conditions are regarded as sulfur donors of group a). These are e.g. Dimorpholyl disulfide (DTDM), tetramethylthiuram disulfide (TMTD) or 2- (N-morpholinyldithio) benzothiazole.
Als Beschleuniger der Mercaptogruppe in b)seien beispielhaft genannt: 2-Mercaptobenzthiazol (MBT), Dibenzothiazyl-disulfid (MBTS) oder das Zinksalz des 2-Mercaptobenzthiazols (ZMBT).Examples of accelerators of the mercapto group in b) are: 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS) or the zinc salt of 2-mercaptobenzothiazole (ZMBT).
Als Beschleuniger der Sulfenamid-Gruppe in b) seien beispielsweise genannt: Benzothiazyl-2-cyclohexylsulfen- amid (CBS), Benzothiazyl-2-tert.-butylsulfenamid (TBBS), Benzothiazyl-2-morpholinsulfenamid (MBS), 2-(N-Morpholinyl-dithio)-benzöthiazol (MBSS) oder Morpholinyl-thiocarbonyl-sulfenmorpholid (OTOS).Examples of accelerators of the sulfenamide group in b) are: benzothiazyl-2-cyclohexylsulfen- amide (CBS), benzothiazyl-2-tert-butylsulfenamide (TBBS), benzothiazyl-2-morpholine sulfenamide (MBS), 2- (N-morpholinyl-dithio) -benzenethiazole (MBSS) or morpholinyl-thiocarbonyl-sulfenmorpholide (OTOS).
Bevorzugt werden MBT, MBTS, CBS, TBBS und MBS.MBT, MBTS, CBS, TBBS and MBS are preferred.
Als konventionelle Zusatzbeschleuniger in c) seien beispielhaft genannt: Tetramethylthiuram-disulfid (TMTD), Tetramethylthiurammonosulfid (TMTM), Zink-N-dimethyldithiocarbamat (ZDMC), Zink-N-diethyl-dithiocarbamat (ZDEC), Zink-N-dibutyldithio-carbamat (ZDBC), Zink-N-ethylphenyldithiocarbamat (ZEPC) oder Zink-N-penta-methylen-dithiocarbamat (Z5MC).Examples of conventional additional accelerators in c) are: tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), zinc-N-dimethyldithiocarbamate (ZDMC), zinc-N-diethyl-dithiocarbamate (ZDEC), zinc-N-dibutylate ZDBC), zinc N-ethylphenyldithiocarbamate (ZEPC) or zinc N-penta-methylene dithiocarbamate (Z5MC).
Beispielhaft seien folgende Verbindungen d) genannt:
- Bis-(Pentachlorphenyl)-disulfid
- Bis-(PentachlorphenyL)-trisulfid
- Bis-(Pentachlorphenyl)-tetrasulfid
- Bis-(Pentachlorphenyl)-dithio-methan
- Bis-(Pentachlorphenyl)-dithio-1,2-ethan 2-(Pentachlorphenyl-dithio)-acetaldehyd-diethylacetal
- Pentachlorphenyl-dithio-2-propan
- Pentachlorphenyl-dithio-1-propan
- Pentachlorphenyl-dithio-butan
- Pentachlorphenyl-dithio-pentan
- Pentachlorphenyl-dithio-hexan
- Pentachlorphenyl-dithio-heptan
- Pentachlorphenyl-dithio-octan Pentachlorphenyl-dithio-(2-ethylhexan) Pentachlorphenyl-dithio-nonan Pentachlorphenyl-dithio-decan Pentachlorphenyl-dithio-undecan Pentachlorphenyl-dithio-dodecan Pentachlorphenyl-dithio-tert.-dodecan Pentachlorphenyl-dithio-cyclobutan Pentachlorphenyl-dithio-cyclohexan Pentachlorphenyl-dithio-cycloheptan Pentachlorphenyl-dithio-cyclooctan Pentachlorphenyl-dithio-cyclononan Pentachlorphenyl-dithio-cycloundecan Pentachlorphenyl-dithio-benzol Pentachlorphenyl-dithio-(2-methylbenzol) Pentachlorphenyl-dithio-(4-methylbenzol) Pentachlorphenyl-dithio-(4-butylbenzol) Pentachlorphenyl-dithio-(4-nonyl-benzol) Pentachlorphenyl-dithio-(4-dodecyl-benzol) Pentachlorphenyl-dithio-(4-tert.butyl-benzol) Pentachlorphenyl-dithio-(4-chlorbenzol) Pentachlorphenyl-dithio-(4-methoxybenzol) Pentachlorphenyl-dithio-(2-hydroxycarbonylbenzol) Pentachlorphenyl-dithio-(2-methoxycarbonylbenzol) Pentachlorphenyl-dithio-(2,3,4-trichlorbenzol) pentachlorphenyl-dithio-(2-trichlormethylbenzol) Pentachlorphenyl-dithio-(2-cyanobenzol) Pentachlorphenyl-dithio-(2-trifluormethylbenzol) Pentachlorphenyl-dithio-(2-nitro-benzol) Pentachlorphenyl-dithio-(4-nitro-benzol) Pentachlorphenyl-dithio-(2,4-dimethylbenzol) Pentachlorphenyl-dithio-(2-ethanol) Pentachlorphenyl-dithio-(2-butanol-(1)) Pentachlorphenyl-dithio-(2-propanol) Pentachlorphenyl-dithio-(3-butanol-(2)) Pentachlorphenyl-dithio-(2-cyclopentanol-(1)) Pentachlorphenyl-dithio-(2-cyclohexanol-(1)) Pentachlorphenyl-dithio-(phenylethanol-2) Pentachlorphenyl-dithio-2(2,2-dimethylethanol-1) Pentachlorphenyl-dithio-acetat Pentachlorphenyl-dithio-benzoat Pentachlorphenyl-dithio-propionat Pentachlorphenyl-dithio-phenylsulfinat Pentachlorphenyl-dithio-(4-chlorphenylsulfinat) Pentachlorphenyl-dithio-essigsäure Pentachlorphenyl-thiophenylsulfinat Pentachlorphenyl-thio-(4-chlorphenylsulfinat) Pentachlorphenyl-dithio-(4-methylphenylsulfinat) Pentachlorphenyl-thio-(4-methylphenylsulfinat) Pentachlorphenyl-dithio-carbonat Pentachlorphenyl-trithio-carbonat Pentachlorphenyl-dithio-phenylsulfit Bis-(pentachlorphenyl-dithio)-1,2-ethan Bis-(pentachlorphenyl-dithio)-1,3-propan Bis-(pentachlorphenyl-dithio)-1,4-butan Bis-(pentachlorphenyl-dithio)-1,2-propan Bis-(pentachlorphenyl-dithio)-1,5-pentan Bis-(pentachlorphenyl-dithio)-1,6-hexan Bis-(pentachlorphenyl-dithio)-1,7-heptan Bis-(pentachlorphenyl-dithio)-1,8-octan Bis-(pentachlorphenyl-dithio)-1,9-nonan Bis-(pentachlorphenyl-dithio)-l,lo-decan Bis-(pentachlorphenyl-dithio)-1,11-undecan Bis-(pentachlorphenyl-dithio)-1,12-dodecan Bis-(pentachlorphenyl-dithio)-1,4-cyclohexan Bis-(pentachlorphenyl-dithio)-1,2-cyclohexan Bis-(pentachlorphenyl-dithio)-1,3-cyclopentan Bis-(pentachlorphenyl-dithio)-1,4-cycloheptan Bis-(pentachlorphenyl-dithio)-1,2-benzol Bis-(pentachlorphenyl-dithio)-1,3-benzol Bis-(pentachlorphenyl-dithio)-1,4-benzol Bis-(pentachlorphenyl-dithio)-2,4-toluol Bis-(pentachlorphenyl-dithiomethyl)-1,2-benzol Bis-(pentachlorphenyl-dithiomethyl)-1,3-benzol Bis-(pentachlorphenyl-dithiomethyl)-1,4-benzol Bis-(4-Methylphenyl)-disulfid Bis-(4-Methylphenyl)-trisulfid Bis-(4-Methylphenyl)-tetrasulfid Bis-(4-Chlorphenyl)-disulfid Bis-(4-Chlorphenyl)-trisulfid Bis-(4-Chlorphenyl)-tetrasulfid Bis-(4-tert.-Butylphenyl)-disulfid Bis-(4-tert.-Butylphenyl)-trisulfid Bis-(4-tert.-Butylphenyl)-tetrasulfid Bis-(4-Methoxy-carbonylphenyl)-trisulfid Bis-(2-Hydroxy-carbonylphenyl)-disulfid Bis-(2-Hydroxy-carbonylphenyl)-trisulfid Bis-(2-Hydroxy-carbonylphenyl)-tetrasulfid Bis-(2-cyanophenyl)-disulfid Bis-(2-Cyanophenyl)-trisulfid Bis-(2-Cyanophenyl)-tetrasulfid Bis-(2,3,4-Trichlorphenyl)-disulfid Bis-(2,3,4-Trichlorphenyl)-trisulfid Bis-(2,3,4-Trichlorphenyl)-tetrasulfid Pentachlorphenyl-dithio-trichlormethan Pentachlorphenyl-dithio-methylbenzol Pentachlorphenyl-dithio-phenylmethan
- Bis-(4-Methoxyphenyl)-disulfid
- Bis-(4-Methoxyphenyl)-trisulfid
- Bis-(4-Methoxyphenyl)-tetrasulfid
- Bis-(2-Nitrophenyl)-disulfid
- Bis-(2-Nitrophenyl)-trisulfid
- Bis-(2-Nitrophenyl)-tetrasulfid
- Bis-(2-Nitro-4-trifluormethylphenyl)-disulfid
- Bis-(Pentachlorphenylthio)-methan
- Bis-(2,4,5-Trichlorphenyl)-trisulfid
- Pentachlorphenyl-dithio-(4-chlorbenzol)
- Pentachlorphenyl-dithio(2-essigsäure-monoglykolester)
- Pentachlorphenyl-dithio-(.2-essigsäure-diethylenglykol- monoester)
- Pentachlorphenyl-dithio-(2-essigsäure-ethylester).
- Bis (pentachlorophenyl) disulfide
- Bis (pentachlorophenyl) trisulfide
- Bis (pentachlorophenyl) tetrasulfide
- Bis (pentachlorophenyl) dithio methane
- Bis (pentachlorophenyl) dithio-1,2-ethane 2- (P entachlorphenyl-dithio) acetaldehyde diethyl acetal
- Pentachlorophenyl dithio-2-propane
- Pentachlorophenyl dithio-1-propane
- Pentachlorophenyl dithio-butane
- Pentachlorophenyl dithio pentane
- Pentachlorophenyl dithio hexane
- Pentachlorophenyl dithio-heptane
- Pentachlorophenyl dithio-octane Pentachlorophenyl-dithio (2-ethylhexane) pentachlorophenyl-dithio-nonane pentachlorophenyl-dithio-decane pentachlorophenyl-dithio-undecane pentachlorophenyl-dithio-dodecane P entachlorphenyl-dithio-tert-dodecane pentachlorophenyl-dithio-cyclobutane pentachlorophenyl-dithio-cyclohexane pentachlorophenyl dithio-cycloheptane pentachlorophenyl-dithio-cyclooctane pentachlorophenyl-dithio-cyclononane pentachlorophenyl-dithio-cycloundecane P entachlorophenyl-dithio-benzene pentachlorophenyl-dithio- (2-methylbenzene) P entachlorophenyl-dithyl-(4-methylbenzene) (4-methylbenzene) butylbenzene) P entachlorophenyl-dithio- (4-nonyl-benzene) P entachlorophenyl-dithio- (4-dodecyl-benzene) pentachlorophenyl-dithio- (4-tert-butyl-benzene) P entachlorophenyl-dithio- (4-chlorobenzene) P entachlorophenyl-dithio- (4-methoxybenzene) P entachlorophenyl-dithio- (2-hydroxycarbonylbenzene) P entachlorophenyl-dithio- (2-methoxycarbonylbenzene) pentachlorophenyl-dithio- (2,3,4-trichlorobenzene) p entachlorophenyl-dithio- (2- trichloromethylbenzene) p entachlorophen yl-dithio- (2-cyanobenzene) P entachlorphenyl-dithio (2-trifluoromethylbenzene) pentachlorophenyl-dithio (2-nitro-benzene) pentachlorophenyl-dithio- (4-nitro-benzene) P entachlorphenyl-dithio (2,4 -dimethylbenzene) pentachlorophenyl-dithio- (2-ethanol) Pentachlorophenyl-dithio- (2-butanol- (1)) pentachlorophenyl-dithio- (2-propanol) pentachlorophenyl-dithio- (3-butanol- (2)) pentachlorophenyl-dithio- (2-cyclopentanol- (1)) pentachlorophenyl- dithio- (2-cyclohexanol- (1)) pentachlorophenyl-dithio- (phenylethanol-2) pentachlorophenyl-dithio-2 (2,2-dimethylethanol-1) pentachlorophenyl-dithio-acetate pentachlorophenyl-dithio-benzoate P entachlorophenyl-dithio-propionate pentachlorophenyl-dithio-phenylsulfinate pentachlorophenyl-dithio- (4-chlorphenylsulfinat) pentachlorophenyl-dithio-acetic acid pentachlorophenyl thiophenylsulfinat P entachlorphenyl-thio (4-chlorphenylsulfinat) pentachlorophenyl-dithio- (4-methylphenylsulfinat) pentachlorophenyl-thio (4-methylphenylsulfinat) pentachlorophenyl-dithio-carbonate pentachlorophenyl trithio-carbonate entachlorphenyl P-dithio-phenylsulfit bis (pentachlorophenyl-dithio) -1,2-ethane, bis (pentachlorophenyl-dithio) -1,3-propane bis (pentachlorophenyl-dithio) - 1,4-butane bis- (pentachlorophenyl-dithio) -1,2-propane bis- (pentachlorophenyl-dithio) -1,5-p entane bis- (pentachlorophenyl-dithio) -1,6-hexane bis- (pentachlorophenyl-dithio) -1,7-heptane bis- (pentachlorophenyl-dithio) -1,8-octane bis- (pentachlorophenyl-dithio) -1, 9-nonane bis- (pentachlorophenyl-dithio) -1, lo-decane bis- (pentachlorophenyl-dithio) -1,11-undecane bis- (pentachlorophenyl-dithio) -1,12-dodecane Bis- (pentachlorophenyl-dithio) -1,4-cyclohexane bis- (pentachlorophenyl-dithio) -1,2-cyclohexane bis- (pentachlorophenyl-dithio) -1,3-cyclopentane bis- (pentachlorophenyl-dithio) -1.4 -cycloheptane bis- (pentachlorophenyl-dithio) -1,2-benzene bis- (pentachlorophenyl-dithio) -1,3-benzene bis- (pentachlorophenyl-dithio) -1,4-benzene bis- (pentachlorophenyl-dithio) -2 , 4-toluene bis (pentachlorophenyl-dithiomethyl) -1,2-benzene bis (pentachlorophenyl-dithiomethyl) - 1,3-benzene-bis (pentachlorophenyl-dithiomethyl) -1,4-benzene bis (4-methylphenyl) -disulfide bis- (4-methylphenyl) -trisulfide bis- (4-methylphenyl) -tetrasulfide bis- (4-chlorophenyl) -disulfide bis- (4-chlorophenyl) -trisulfide bis- (4-chlorophenyl) -tetrasulfide bis- ( 4-tert-butylphenyl) disulfide bis- (4-tert-butylphenyl) trisulfide bis- (4-tert-butylphenyl) tetrasulfide bis- (4-methoxycarbonylphenyl) trisulfide bis- (2-hydroxy -carbonylphenyl) -disulfide bis- (2-hydroxycarbonylphenyl) -trisulfide bis- (2-hydroxycarbonylphenyl) -tetrasulfide bis- (2-cyanophenyl) -disulfide bis- (2-cyanophenyl) -tri sulfide bis (2-cyanophenyl) tetrasulfide bis (2,3,4-trichlorophenyl) disulfide bis (2,3,4-trichlorophenyl) trisulfide bis (2,3,4-trichlorophenyl) tetrasulfide pentachlorophenyl -dithio-trichloromethane pentachlorophenyl-dithio-methylbenzene pentachlorophenyl-dithio-phenylmethane
- Bis (4-methoxyphenyl) disulfide
- Bis (4-methoxyphenyl) trisulfide
- Bis (4-methoxyphenyl) tetrasulfide
- Bis (2-nitrophenyl) disulfide
- Bis (2-nitrophenyl) trisulfide
- Bis (2-nitrophenyl) tetrasulfide
- Bis (2-nitro-4-trifluoromethylphenyl) disulfide
- Bis (pentachlorophenylthio) methane
- Bis (2,4,5-trichlorophenyl) trisulfide
- Pentachlorophenyl-dithio- (4-chlorobenzene)
- Pentachlorophenyl dithio (2-acetic acid monoglycol ester)
- Pentachlorophenyl-dithio - (. 2-acetic acid-diethylene glycol monoester)
- Pentachlorophenyl dithio (2-acetic acid ethyl ester).
Die genannten Verbindungen sind teilweise neu und teilweise literaturbekannt. Sie lassen sich nach literaturbekannten Verfahren herstellen, z.B. R. Otto, Journal für praktische Chemie (2) 37, 208; oder analog zur US-Patentschrift 2 695 898.Some of the compounds mentioned are new and some are known from the literature. They can be produced by processes known from the literature, e.g. R. Otto, Journal of Practical Chemistry (2) 37, 208; or analogous to US Pat. No. 2,695,898.
Die erfindungsgemäBen Vulkanisationssysteme weisen Vorteile auf hinsichtlich Reversionsbeständigkeit nach längerer Vulkanisationszeit und/oder hohen Vulkanisationstemperaturen (z.B. 45 Min. bei 180°C), hinsichtlich mechanischer Werte wie Spannungswert, Zugfestigkeit, Bruchdehnung, Härte, Elastizität, Weiterreißfestigkeit, Zermürbungsbeständigkeit, Ermüdungsbeständigkeit, innerer Wärmebildung (heat build-up), dynamischem Fließen und Abrieb. Die Einzelkomponenten des Vulkanisationssystems können den Dien-Kautschuken bzw. Kautschukmischungen vor dem Vulkanisieren entweder getrennt oder in Form eines Gemisches oder einer Kautschuk-Beschleuniger-Vormischung (vgl.: Ullmann's Encyklopädie der techn. Chemie, 3. Auflage, Verlag Urban & Schwarzenberg, München-Berlin 1957, Band 9, S. 364) zugesetzt werden.The vulcanization systems according to the invention have advantages in terms of resistance to reversion after a longer vulcanization time and / or high vulcanization temperatures (for example 45 minutes at 180 ° C.), in terms of mechanical values such as tension value, tensile strength, elongation at break, hardness, elasticity, tear resistance, wear resistance, fatigue resistance, internal heat generation ( heat build-up), dynamic flow and abrasion. The individual components of the vulcanization system can either separate the diene rubbers or rubber mixtures before vulcanization or in the form of a mixture or a rubber accelerator premix (see: Ullmann's Encyklopadie der techn. Chemie, 3rd edition, Verlag Urban & Schwarzenberg, Munich -Berlin 1957, Volume 9, p. 364) can be added.
Als Synthesekautschuk aus halogenfreien Dienen seien beispielsweise genannt:
- Polyisopren, Polybutadien, Styrol-Butadien-Kautschuk, Nitrilkautschuk und deren Verschnitte.
- Polyisoprene, polybutadiene, styrene-butadiene rubber, nitrile rubber and their blends.
Die Dien-Kautschuke können alle. üblichen Zusätze wie Füllstoffe, insbesondere Ruße, Mineralöle, Weichmacher, Klebrigmacher, Beschleunigungsaktivatoren, insbesondere Stearinsäure, Wachse, Alterungsschutzmittel-, Ozonschutzmittel, Treibmittel, Farbstoffe, Pigmente enthalten.The diene rubbers can do it all. usual additives such as fillers, in particular carbon blacks, mineral oils, plasticizers, tackifiers, acceleration activators, in particular stearic acid, waxes, anti-aging agents, anti-ozone agents, blowing agents, dyes, pigments.
Füllstoffe, wie die in der kautschukverarbeitenden Industrie verwendeten Rußsorten, weiterhin Kieselsäure, insbesondere feinteilige, in der Gasphase gewonnene Kieselsäure, sowie hydrophobische Kieselsäure und feinteilige Metalloxide, einschließlich Mischoxide und Oxid-Gemische, sind wertvolle Mischungsbestandteile.Fillers such as the types of carbon black used in the rubber processing industry, as well as silica, in particular fine-particle silica obtained in the gas phase, and hydrophobic silica and fine-particle metal oxides, including mixed oxides and oxide mixtures, are valuable components of the mixture.
Die Vulkanisation der Dien-Kautschuke wird im allgemeinen bei Temperaturen zwischen 100°C und etwa 300°C, bevorzugt bei 140 - 240°C, durchgeführt. Hierfür können alle in der Technik üblichen Vulkanisationsverfahren wie Pressenheizung, Heizung mit Heißdampf, Heißluft, Salzbad, Fließbett, Ultrahochfrequenz und Dampfrohr verwendet werden. Die Erfindung sei durch folgende Beispiele erläutert:
zeigt den Vergleich zwischen einem Semi-Efficient-System (1), das nur Schwefel und MBS enthält, einem System (2), das Zinkdibutyldithiophosphat als Zusatz enthält, und einem erfindungsgemäßen System (3), das Pentachlorphenyltetrasulfid enthält. In einem Innenmischer wurde aus folgenden Bestandteilen eine Kautschukvormischung angefertigt:
Auf einem Laborwalzwerk werden folgende Bestandteile nachgemischt:
Mit den folgenden Bestandteilen wurde im Innenmischer eine Kautschukvormischung hergestellt:
Auf einem Laborwalzwerk wurden folgende Mischungen hergestellt:
In der folgenden Tabelle sind die durchgeführten Prüfungen und deren Ergebnisse zusammengestellt:
Das erfindungsgemässe Vulkanisationssystem 2 zeigt deutliche Vorteile vor dem Vergleichssystem 2 hinsichtlich Reversionsbeständigkeit nach Übervulkanisation bei 180°C.The vulcanization system 2 according to the invention has clear advantages over the comparison system 2 with regard to resistance to reversion after over-vulcanization at 180 ° C.
zeigt einen Vergleich zwischen einem Semi-Efficient System (1), das nur Schwefel und MBS enthält, und einem erfindungsgemäßen System (2), das als Zusatz Pentachlorphenyl-disulfid enthält. In einem Innenmischer wurde aus folgenden Bestandteilen eine Kautschukvormischung angefertigt:
Auf einem Laborwalzwerk wurden folgende Bestandteile nachgemischt:
In einem Innenmischer wurde aus den in Beispiel 3 angeführten Bestandteilen eine Kautschukvormischung auf Basis Naturkautschuk hergestellt. Auf einem Walzwerk wurden nachgemischt:
- 1 Bis-(Pentachlorphenyl)-disulfid 1 bis (pentachlorophenyl) disulfide
- 2 Bis-(Pentachlorphenyl)-trisulfid 2 bis (pentachlorophenyl) trisulfide
- 3 Bis-(Pentachlorphenyl)-tetrasulfid 3 bis (pentachlorophenyl) tetrasulfide
- 4 Pentachlorphenyl-dithio-2-ethanol4 pentachlorophenyl-dithio-2-ethanol
- 5 Pentachlorphenyl-dithiocyclohexan5 pentachlorophenyl dithiocyclohexane
- 6 Pentachlorphenyl-dithio-trichlormethan6 pentachlorophenyl-dithio-trichloromethane
- 7 (Pentachlorphenyl-dithio)-acetaldehyd-diethylacetal7 (pentachlorophenyl dithio) acetaldehyde diethylacetal
- 8 Bis-(pentachlorphenyl-dithio)-1,3-propan8 bis (pentachlorophenyl dithio) -1,3-propane
- 9 Pentachlorphenyl-dithio-2-propan9 pentachlorophenyl-dithio-2-propane
- lo Pentachlorphenyl-dithio-methanlo pentachlorophenyl-dithio-methane
- 11 Bis-(pentachlorphenyl-dithio)-1,2-propan11 bis (pentachlorophenyl dithio) -1,2-propane
- 12 Pentachlorphenyl-dithio-1-propan12 pentachlorophenyl-dithio-1-propane
- 13 Pentachlorphenyl-dithio-phenyl-methan13 pentachlorophenyl dithiophenyl methane
- 14 Pentachlorphenyl-trithiocarbonat14 pentachlorophenyl trithiocarbonate
- 15 Bis-(2-Methoxycarbonyl-phenyl)-trisulfid 15 bis (2-methoxycarbonylphenyl) trisulfide
- 16 Bis-(2,4,5-trichlorphenyl)-disulfid 16 bis (2,4,5-trichlorophenyl) disulfide
- 17 Pentachlorphenyl-dithio-(4-chlorbenzol)17 pentachlorophenyl-dithio- (4-chlorobenzene)
- 18 Pentachlorphenyl-dithio-benzol18 pentachlorophenyl-dithio-benzene
- 19 Pentachlorphenyl-dithio-(4-methyl-benzol)19 pentachlorophenyl-dithio- (4-methyl-benzene)
- 2o Bis-(2-Nitrophenyl)-disulfid2o bis (2-nitrophenyl) disulfide
- 21 Pentachlorphenyl-dithio-(2-mitrobenzol)21 pentachlorophenyl-dithio- (2-mitrobenzene)
- 22 Bis-(2-Nitrophenyl)-trisulfid22 bis (2-nitrophenyl) trisulfide
- 23 Pentachlorphenyl-dithio-(4-methylphenylsulfinat)23 pentachlorophenyl dithio (4-methylphenyl sulfinate)
- 24 Pentachlorphenyl-thio-(4-methylphenylsulfinat)24 pentachlorophenyl thio (4-methylphenyl sulfinate)
- 25 Bis-(2-Hydroxycarbonyl-phenyl)-tetrasulfid 25 bis (2-hydroxycarbonylphenyl) tetrasulfide
- 26 Pentachlorphenyl-2-(essigsäuremonoglykolester)26 pentachlorophenyl-2- (acetic acid monoglycol esters)
- 27 Pentachlorphenyl-2-(essigsäure-diethylenglykol-monoester)27 pentachlorophenyl-2- (acetic acid-diethylene glycol monoester)
- 28 Pentachlorphenyl-dithio-(2-essigsäureethylester)28 pentachlorophenyl-dithio- (2-ethyl acetate)
- 29 Pentachlorphenyl-dithioacetat29 pentachlorophenyl dithioacetate
- 3o Pentachlorphenyl-thioacetat3o pentachlorophenyl thioacetate
- 31 Pentachlorphenyl-thiobenzoat31 pentachlorophenyl thiobenzoate
- 532 Pentachlorphenyl-thio-propionat532 pentachlorophenyl thio propionate
Claims (6)
Alkyl mit C1-C12 und Cycloalkylen von C4-C12, das gegebenenfalls substituiert ist durch -OH und/oder Alkoxy mit C1-C4 im Alkoxy-Rest,
Benzyl oder Trichlormethyl darstellt, wobei die Summe der Komponenten a - d) 100 beträgt.
Alkyl with C 1 -C 12 and cycloalkylene of C 4 -C 12 , which is optionally substituted by -OH and / or alkoxy with C 1 -C 4 in the alkoxy radical,
Represents benzyl or trichloromethyl, the sum of components a - d) being 100.
getrennt oder gleichzeitig dem Kautschuk zugibt und anschließend in üblicher Weise vulkanisiert.4. Process for the vulcanization of natural and / or synthetic rubber from halogen-free dienes in the presence of sulfur and / or sulfur donors, vulcanization accelerators and, if appropriate, conventional additives, characterized in that
separately or simultaneously added to the rubber and then vulcanized in the usual manner.
dem Kautschuk getrennt oder gleichzeitig zugibt und anschließend in üblicher Weise vulkanisiert.5. The method according to claim 4, characterized in that one
separately or simultaneously added to the rubber and then vulcanized in the usual manner.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT81102569T ATE14229T1 (en) | 1980-04-17 | 1981-04-06 | METHOD OF PREVENTING REVERSION IN THE MANUFACTURE OF RUBBER VULCANISATES. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19803014717 DE3014717A1 (en) | 1980-04-17 | 1980-04-17 | VULCANIZATION SYSTEM, THIS CONTAINING RUBBER MIX, AND A METHOD FOR VULCANIZATION |
DE3014717 | 1980-04-17 |
Publications (2)
Publication Number | Publication Date |
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EP0038459A1 true EP0038459A1 (en) | 1981-10-28 |
EP0038459B1 EP0038459B1 (en) | 1985-07-10 |
Family
ID=6100240
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP81102569A Expired EP0038459B1 (en) | 1980-04-17 | 1981-04-06 | Process for the prevention of reversion during the manufacture of rubber vulcanisates |
Country Status (8)
Country | Link |
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US (1) | US4340695A (en) |
EP (1) | EP0038459B1 (en) |
JP (1) | JPS56159235A (en) |
AT (1) | ATE14229T1 (en) |
BR (1) | BR8102367A (en) |
CA (1) | CA1165750A (en) |
DE (2) | DE3014717A1 (en) |
ES (1) | ES501348A0 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0178444A2 (en) * | 1984-10-19 | 1986-04-23 | Degussa Aktiengesellschaft | Bis-(2-ethylamino-4-diethylamino-s-triazin-6-yl)tetrasulfide, process for its preparation and use, and vulcanisable mixtures containing it |
EP0239816A2 (en) * | 1986-04-01 | 1987-10-07 | Degussa Aktiengesellschaft | N,N'-substituted bis-(2,4-diamino-s-triazin-6-yl)-tetrasulphides and their disproportionation products, process for their preparation and their use in vulcanisable rubber mixtures |
EP0258676A2 (en) * | 1986-09-04 | 1988-03-09 | Thomas Swan and Co. Ltd | Process for the preparation of mixtures of sulphur-containing triazine compounds |
EP2711198A1 (en) * | 2012-09-24 | 2014-03-26 | LANXESS Deutschland GmbH | Polysulphide additives, process for their preparation and their use in rubber mixtures |
WO2014044514A1 (en) * | 2012-09-24 | 2014-03-27 | Lanxess Deutschland Gmbh | Polysulphide additive, method for production thereof, and use thereof in rubber mixtures |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5817132A (en) * | 1981-07-08 | 1983-02-01 | モンサント・ヨ−ロツプ・ソシエテ・アノニム | Organic thiosulfates and thiosulfonates |
EP0140298B1 (en) * | 1983-10-21 | 1987-01-28 | Ciba-Geigy Ag | Substituted 4-hydroxybenzylthioaldehydes and ketones |
US4618440A (en) * | 1983-10-21 | 1986-10-21 | Ciba-Geigy Corporation | Substituted 4-hydroxybenzylthio aldehyde and ketone stabilizers |
US5770632A (en) * | 1994-06-25 | 1998-06-23 | Sekhar; Balachandra Chakkinggal | Reclaiming of elastomeric materials |
JPH0841107A (en) * | 1994-06-25 | 1996-02-13 | Sti K Polymers Sdn Bhd | Method for reclaiming used vulcanized elastomeric material and composition for reclamation |
JP4921534B2 (en) * | 2009-10-13 | 2012-04-25 | Sriスポーツ株式会社 | Solid golf balls |
EP2517898A1 (en) * | 2011-04-29 | 2012-10-31 | Lanxess Deutschland GmbH | Rubber mixtures containing silicic acids with additives containing sulphur |
EP2671727A1 (en) * | 2012-06-06 | 2013-12-11 | LANXESS Deutschland GmbH | Rubber mixtures containing silicic acids with additives containing sulphur |
EP2727907B1 (en) * | 2012-10-30 | 2015-05-13 | LANXESS Deutschland GmbH | Polysulphide mixture, process for its preparation and use of the polysulphide mixture in rubber mixtures |
Citations (4)
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DE1231236B (en) * | 1961-12-30 | 1966-12-29 | Progil | Process for the preparation of oil-soluble, resinous, chlorinated or brominated, optionally alkylated, phenyl polysulphides |
US3354131A (en) * | 1967-03-22 | 1967-11-21 | Monsanto Co | Inhibiting pre-vulcanization with polysulfides |
Family Cites Families (9)
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US2695898A (en) * | 1949-12-27 | 1954-11-30 | Bayer Ag | Rubbery polymers plasticized with thio derivatives of polychlorobenzenes |
US3630940A (en) * | 1969-04-28 | 1971-12-28 | Goodyear Tire & Rubber | 2-mercaptobenzothiazole/tetraalkylthiuram disulfide mixture |
US3579460A (en) * | 1969-06-16 | 1971-05-18 | Joseph Edward Kerwood | Sulfenamide compositions stabilized by organic disulfides |
US3678017A (en) * | 1970-04-07 | 1972-07-18 | Goodyear Tire & Rubber | Inhibiting premature vulcanization of rubbers |
DE2120288C3 (en) * | 1971-04-26 | 1980-02-14 | Bayer Ag, 5090 Leverkusen | Process for vulcanizing natural and synthetic rubbers made from halogen-free dienes |
US3919179A (en) * | 1972-04-18 | 1975-11-11 | Goodyear Tire & Rubber | Three-component accelerator system |
US4012332A (en) * | 1974-01-30 | 1977-03-15 | American Cyanamid Company | Rubber vulcanization accelerator composition |
US4116855A (en) * | 1977-03-18 | 1978-09-26 | American Cyanamid Company | Stabilized accelerator composition for rubber |
JPS5953297B2 (en) * | 1979-08-28 | 1984-12-24 | 住友ゴム工業株式会社 | thread rubber |
-
1980
- 1980-04-17 DE DE19803014717 patent/DE3014717A1/en not_active Withdrawn
-
1981
- 1981-04-06 DE DE8181102569T patent/DE3171298D1/en not_active Expired
- 1981-04-06 AT AT81102569T patent/ATE14229T1/en active
- 1981-04-06 EP EP81102569A patent/EP0038459B1/en not_active Expired
- 1981-04-08 US US06/252,051 patent/US4340695A/en not_active Expired - Fee Related
- 1981-04-14 JP JP5514581A patent/JPS56159235A/en active Pending
- 1981-04-14 ES ES501348A patent/ES501348A0/en active Granted
- 1981-04-15 BR BR8102367A patent/BR8102367A/en unknown
- 1981-04-15 CA CA000375535A patent/CA1165750A/en not_active Expired
Patent Citations (4)
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BE615538A (en) * | ||||
US3217044A (en) * | 1960-07-21 | 1965-11-09 | Hoechst Ag | Highly chlorinated aryl sulfides and process for the manufacture thereof |
DE1231236B (en) * | 1961-12-30 | 1966-12-29 | Progil | Process for the preparation of oil-soluble, resinous, chlorinated or brominated, optionally alkylated, phenyl polysulphides |
US3354131A (en) * | 1967-03-22 | 1967-11-21 | Monsanto Co | Inhibiting pre-vulcanization with polysulfides |
Non-Patent Citations (1)
Title |
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CHEMICAL ABSTRACTS, Band 57, Nr. 12, 10. Dezember 1962, spalte 15312g Columbus, Ohio, U.S.A. & BE - A - 615 538 (Bunawerke Huels GmbH) 23-03-1962 * Zusammenfassung * * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0178444A2 (en) * | 1984-10-19 | 1986-04-23 | Degussa Aktiengesellschaft | Bis-(2-ethylamino-4-diethylamino-s-triazin-6-yl)tetrasulfide, process for its preparation and use, and vulcanisable mixtures containing it |
EP0178444A3 (en) * | 1984-10-19 | 1987-04-15 | Degussa Aktiengesellschaft | Bis-(2-ethylamino-4-diethylamino-s-triazin-6-yl)tetrasulfide, process for its preparation and use, and vulcanisable mixtures containing it |
EP0239816A2 (en) * | 1986-04-01 | 1987-10-07 | Degussa Aktiengesellschaft | N,N'-substituted bis-(2,4-diamino-s-triazin-6-yl)-tetrasulphides and their disproportionation products, process for their preparation and their use in vulcanisable rubber mixtures |
EP0239816A3 (en) * | 1986-04-01 | 1989-05-10 | Degussa Aktiengesellschaft | N,n'-substituted bis-(2,4-diamino-s-triazin-6-yl)-tetrasulphides and their disproportionation products, process for their preparation and their use in vulcanisable rubber mixtures |
EP0258676A2 (en) * | 1986-09-04 | 1988-03-09 | Thomas Swan and Co. Ltd | Process for the preparation of mixtures of sulphur-containing triazine compounds |
EP0258676A3 (en) * | 1986-09-04 | 1989-05-10 | Thomas Swan and Co. Ltd | Process for the preparation of mixtures of sulphur-containing triazine compounds |
EP2711198A1 (en) * | 2012-09-24 | 2014-03-26 | LANXESS Deutschland GmbH | Polysulphide additives, process for their preparation and their use in rubber mixtures |
WO2014044514A1 (en) * | 2012-09-24 | 2014-03-27 | Lanxess Deutschland Gmbh | Polysulphide additive, method for production thereof, and use thereof in rubber mixtures |
Also Published As
Publication number | Publication date |
---|---|
EP0038459B1 (en) | 1985-07-10 |
DE3171298D1 (en) | 1985-08-14 |
ATE14229T1 (en) | 1985-07-15 |
ES8203096A1 (en) | 1982-03-01 |
ES501348A0 (en) | 1982-03-01 |
CA1165750A (en) | 1984-04-17 |
DE3014717A1 (en) | 1981-10-22 |
BR8102367A (en) | 1981-12-22 |
JPS56159235A (en) | 1981-12-08 |
US4340695A (en) | 1982-07-20 |
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